Chromiable brown disazo dyestuffs



Patented Sept. 20, 1927.

UNITED STATES" 1,643,222 PATENT OFFICE.

WILHELM NEELMEIEB, OI LEVERKUSEN, THEODOR NOCKEN, OF WIESDOEE, NEAR, COLOGNE-ON-THE-BHINE, AND WERNER REBNER, E. COLOGNE-MUHLHEIM, GER- MANY, ASSIGNORS TO GRASSELLI DYESTUFFCOBPORATION, 013: NEW YORK, N. .'Y., i

A COBPQRATION OF DELAWARE.

CHROMIAIBLE BROWN DISAZO DYESTUFES.

Ro Drawing. Application filed April 22, 1926, Serial 110,103,961, and in Germany April 28, 1925.

Our invention consists in new disazodyestuffs which printed with chromium com pounds upon cotton, yield exceedingly fast brown shades, and in the process of producing these compounds. In the German Patents 51,504, 59,081, 58,415 there are described disazodyestuifs which are obtained by combining diazotized aromatic amino carboxylic acids such as m aminobenzoic acid, aminophthalic acid,

aminosalicylic acid etc. with l-naphthylamine, diazotizing the aminoazo compound obtained and coupling with any desired coupling compound. If for the latter o-hys droxycarboxylic acids are used dyestuffs are obtained which produce brown shades when printed with chromium acetate. ,None of these products has, however, found technical application. Their solubility is in many 2 cases quite insuflicient forcotton printing and the second coupling with o-hydroxy carboxylic acids is furthermore very imperfect.

in which R is the radicle of an aromatic amino carboxylic acid and includes their sulfonic acids, R is the radicle'of a Cleves acid and R" is the radicle of an ortho-hydroxycarboxylic acid. The process of pro- 5 ducing these novel disazodyestufl's consistsessentially in diazotizin aromatic aminocarboxylic acids, coupling the diazocompound obtained with a Oleves acid, rediazotizing and coupling with an ortho-hydroxycarboxylic acid.

The use of Cleves acids in the above type of disazodyestuffs produces quite an unexpected and exceedingly valuable effect. The solubility of the new products is excellent and the second coupling proceeds smoothly with superior yields which renders their technical production. economically possible.

These novel dyestuffs are in form of their I alkali metal salts dark reddish brown crystalline powders, they are soluble in water withusually an orange color: and are soluble in concentrated sulfuric acid with blue to green colors. Printed on cotton with chromium acetate they yield brown shades having a high degree of fastne'ss to Washing, chlorine and light heretofore unknown in chromium printing. These new'dyestuffs enable one to produce by chromium print ing brown dyeings which up to now could only be produced with these fastness properties by the use of a few Vat colors. I

To further illustrate our invention the following examples are given, the parts being by weight. Ewample 1.l8,1 parts of4-aminophthalic acid are diazotized in the usual manner and coupled with a solutionof 22,3 parts of 1-naphthylamine-G-sulfonic acid in 500 parts of water and the solution made organic acid by neutralizing the mineral acidity with sodium acetate. The reaction product is stirred for several hours until the coupling is completed;

The reaction mass is then heated to dis-. solve the dyestufi, treated with hydrochloric acid, in amount suflicient to render the reaction product acid to congo paper; the" aminoazocompound crystallizes out oncooling. It is filtered off and then dissolved in 250 parts of hot water made alkaline with a little caustic soda. 75 parts of a 10 per cent. sodium nitrite solution are then added, the mass cooled to 5 C. and at once 50 parts of concentrated hydrochloric acid added. The diazocompound crystallizes out, it is filtered off in vacuo and added to a solution of 15,2 parts .m-cresotinic acid in 150 parts V water containing 30 parts of soda ash, and

cooled to-S to 0 C. The mass is stirred for several hours, then heated to 80 C. and

salted out with sodium chloride. The dye stuff is thenfiltered ofl' andldried in the usual manner. his a reddish-brown powder, soluble in water-with an orange color crystalline pow er, soluble in water with an and soluble in concentrated sulfuric acid with a green color. The most probable for- 'mula for the free dyestufi' is:

Hooc

soar

Printed with chromium acetate on cotton it roduces beautiful brown shades of superior astness to chlorine, washing and hght. Afterchro'med on wool it produces a reddish brown dyeing fast to milling and partlcularly fast to light.

EmampZe Q.-233 parts '3-amino-5-sulfo-2- con- hydroxy-benzoic acid are diazotized in the usual manner and coupled in acetic acid solution with 223 parts of 1-naphthylaminefi-sulfonic acid. The reactionmm is made soda alkaline and the monoazodyestuflf salted out, it is then filtered OE and redissolved in 3000 parts ofwater. ,Themass is cooled to 0 C. and 69lparts of sodium nitrite and 500 parts 19,5 hydrochloric acid added at once. The diam-compound crystallizes out;

it is filtered off, sludged with 1000 parts icewater and a neutral solution of7150 parts. of salicylic acid in 200 parts water is added. After cooling to 5 C. there are added quickly 300 parts of soda ash and 150 parts .40 caustic soda solution. The coupling is shortly finished.- The dyestufl! c'rystalhzes' directly from the reaction mass and is oi}. tained in substantially ure form b filtering it ofi. It is when (fly, a r'edd' -brown orange red color and soluble in concentrated sulfuric acid with ablue color. It has'in the freestate most probably the formula J no.5 -N N-N-QOH v coon or: p

con sou:

Printed with. chromium compounds on 'cotton it yields a reddish-brown of good light, washing and chlorine-fast'ness properties which com are favorably with dyeingsobtained wit an known Inda'nthrene color. Wool is dyed- 'rectly orange brown shades which by afterchroming are changed to reddish-brown. of superiorlight and milling :Eastness.

We claim 2-:

1. In process of.

' d estufis suitable otcotton printing with ortho-hydroxy-carboxyhc romium compounds, the steps compris' cou lin an aromatic 11c aci Witt t1 eves acid, 'e mow azocom Oundiormodami cogpling with an general formula inyhich R is the radicle of an aromatic amino-carboxylic acid, R the radicle of a Cleves acid and R" the radicle of an orthohydroxy-carboxylic acid, which dyestuffs produce when printed withchromium compounds on cotton exceedingly fast brown shades.

5. As new products disazodyestufis of the R-N-N N-N-R" {process of producing a brown- SO: in which R is the radicle of an aromatic amino-carboxylic acid and R" the-radicle of an orthro-hy'drox ybarboxylic acid, which dyestuffs produce when printed with chromiumcompounds on cotton exceedingly fast brown shades.

6; As a new product the disazodyestufl lfiavin in the free state most probably the orm Hole --1 N-NQOE I coon on 'O0 is sor which is substantially identical with the 'roduct: obtained by coupling 3-diazo-5-sulo-2-hydro -benzoic acid with 1-naphthylamine-6'- ul onic acidi rediazotizing the mon oazod estufi forme and coupling with salicy '0 acid, which in form of its alkali metal salt is areddish-brown powder, soluhis in water with an orange-red color, solu- .blein concentrated sulfuric acid with a blue ice color and when printed on cotton with chromium compoundsyields enceedingly brown shades.

In testimony our hands; v a WILHELM NEELMEIER.

' 'THEODOR NOCKEN.

whereof we have hereunto set 

